Resinous products from hf acidsoluble oils



Sept. 1l, 1951 l.. c. MoRRls RESINOUS PRODUCTS 'FROM HF ACID-SOLUBLEOILS Filed sept. 25, 194e INVENToR L C. MORRIS. BY y 17.

ATTORNEYS III Patented Sept. 11, 1951l UNITED STATE RESINOUS PRODUCTSFROM HF ACID- SOLUBLE OILS Lloyd Clayton Morris, Bartlesville, Okla.,assignor to Phillips Petroleum Company, a corporation of DelawareApplication september 2s, 1946, serial N6. 698,638

This invention relates to the conversion of hydrocarbons. In one aspectthis invention relates to the conversion of acid-soluble oils. Inanother aspect this invention relates to the utilization of acid-solubleoils obtained as a byproduct from a hydrofluoric 'acid alkylationprocess. In still another aspect this invention relates'to themanufacture of a solid hydrocarbon resin.

In the conversion of hydrocarbons in the presence of inorganic acidcatalysts, -such as hydrofluoric acid or sulfuric acid, acid-solubleoils are formed as by-products of the conversion reaction and arepresent in the acid phase of the conversion process.' Perhaps one of themost important of such conversion processes in which acidsoluble oilsare formed is the alkylation of hydrocarbons in the presence ofhydrofluoric acid as the catalyst. This so-called hydroiluoric acidalkylation involves the reaction of an isoparailin, particularlyisobutane and/or isopentane, with an alkylating reactant, particularlyan olefin, such as propylene, various butylenes, various amylenes andother higher boiling olens, to produce normally liquid parafns whichgenerally 8 Claims. (Cl. 260-96) have high octane numbers and are quitevaluable asconstituents of aviation fuel. In such,;alkyla tion processesthe reactants are intimately contacted at temperatures between about 50and about 150 F. and under suiilcient pressure to maintain reactants inthe liquid phase with liquid concentrated hydrouoric acid for a reactionperiod ranging from about 1 to about 30 minutes. The mole ratio ofparaffin to olefin in the feed is usually from about 3:'1 to about 20:1,

and may be as high as 100:1 in the reaction zone itself. The resultingreaction eilluent is passed to a settling zone wherein a liquidhydrocarbonrich phase and a heavier liquid hydrofiuoric'acidrich phaseare formed and separated.

The hydrocarbon phase from the settling zone is uien subjected tofractional distillation to remove hydrogen uoride dissolved therein,which is generally present to the extent of about l to about 3 per centby volume. After removal of the hydrogen fluoride from the hydrocarbonphase, the remaining portion of the hydrocarbon phase is passed to aseparation or distillation zone for the removal and recovery of` thealkylation product. This product of the process comprises,4

in general, alkylated hydrocarbons, such as isooctanes, heptanes andhexanes and some pentanes, of high anti-knock quality.

The acid phase from the separation zone is recycled directly to thealkylation reaction zone;

2 however, since the acid phase becomes contaminated with water andother impurities, a portion of the acid phase is passed to apurification system for the removal of water and other impurities. Oneof the impurities besides water which is removed from the acid phase inthe purification system is the so-called acid-soluble oils. Theseacid-soluble oils, which are referred to in the copending application ofFrederick E. Frey, Serial No. 429,961, filed February 7, 1942, now U. S.Patent 2,494,867, and which are a by-product of the alkylation reaction,vary considerably in composition but are, in general, normally liquidmaterials and are soluble in hydrogen fluoride andpartially soluble inwater and in hydrocarbons. They appear tohave a tendency to re- A ducethe catalytic activity of the hydrofluoric acid and to-vary the courseof alkylation reaction, thus necessitating their removal from the acidphase of the alkylation process. The amount of these acid-soluble oilswhich is formed may amount to about 1 to 2 'percent to as high as about10 per cent of the acid phase. A typical acid-soluble oil has thefollowing characteristics:

I Table I A. P..I. gravity@ F 22.7 Viscosity, S. U. S. F. 390 Viscosity,S. U. S. 210 F 6l Flash point, C. o. c., PF 205 Firepoint, C. O. C., F220 .Pour point, "F 5+ Total solids, A. s. T. M. D154, percent 67 IodineNo., Wijs (pure oil modif.)

. g. 12/100 g. oil 167 Polymer color-.. 2- Free HF none Water, percenttrace Sulfur, percent 0.011 vCombined vfluorine, percent 0.081

' in which hydrogen fluoride and water pass overhead as a vapor andacid-solubleoils containing somefree hydrogenfluoride 'are removed as abot- 3 tom product. The hydrogen uoride and Water overhead is passed tothe second distillation column in which substantially anhydrous hydrogenfluoride is removed as an overhead fraction and a liquid azeotropicmixture of Water and hydrogen fluoride isV removed as a bottom fraction.The anhydrous hydrogen fluoride overhead fraction is recycled to thereaction zone and the azeotropic mixture of hydrogen fiuoride and wateris usually discarded or further treated to recover the hydrogen fluoridetherefrom. In another method for removing water and acid-soluble oilsfrom the acid phase, a single distillation of the acid phase iseffected. Substantiallyfianhydrous hydrogen f fluoride is removedoverhead from the distillation and acid-soluble oils, Water and somehydrogen iiuoride are removed as a bottom product of the distillation.The acid-soluble oils are separated from the bottom product by settling,which settling results in the formation of an acid-soluble oil phase anda heavier aqueous hydrogen uoride phase. The recovery of acid-solubleoils by this latter method is more fully described in the copendingapplication of D. E. Bergen, Serial No. 672,475, filed May 27, 1946, nowU. S. Patent 2,493,384. This invention constitutes a process forutilization of the acid-soluble oil by-product recovered in the acidpurification system.

The object of this invention is to provide a novel hydrocarbonconversion process.

Another object is to provide a process for the conversion ofacid-soluble oilsin the presence of a catalyst. I

Another object of this invention is to provide a method for decreasingthe operational and man terial cost of an alkylation process.

Still a further object of this invention is to provide an integratedalkylation process in which an alkylation by-product of a firstalkylation reaction is converted in a second reaction to produce avaluable product. v

Still another lobject of this invention is to provide a processfor themanufacture of a high quality solid hydrocarbon resin.

It is yet another object Ato provide a novel resinous composition.

Yet a further object is to provide a process for the hydrogenation ofacid-soluble oils.

Further objects and advantages will become apparent to those 'skilled inthe art from the accompanying description and disclosure.

According to this invention a normally liquid acid-soluble oil fractionis distilled to remove volatile components and leave a solid resinousresidue. The'resinous residue obtained by the distillation of anacid-soluble oil fraction is clear and brown in color and isnsubstantially completely soluble in parafnic and aromatic hydrocarbonsolvents. Hardness of the'resin produced according to this inventiondepends to a large extent upon the distillation conditions, but, ingeneral, ranges from a relatively plastic to a relatively brittle mass.The softer resins are slightly tacky while in the harder resins thisproperty is not apparent. In general the iodine number (Wijs method) isin the range between about 140 and about 180 and will generally averagebetween about 150 and about 165. Such resins form a clear solution indrying oils, such as linseed oil, and may be used in the compounding ofpaint.

The distillation of the normally liquid acidsoluble oil fraction, suchas that obtained as a by-product of the acid purification of analkylation process using a fluorine-containingcatalyst, is effected at apressure less than about 100 mm.

4 of mercury and preferably between about 5 arid about mm. of mercuryand at a kettle temperature, which depends upon the pressure and uponextent of removal of volatile components, between about 350 and about600 F. The yield plastic product and about per cent for a hard brittleresinous product. In other Words between about 55 and about 80 per centof the acid-soluble r Aoil fraction is distilled overhead during thedisout hydrogenation.

tillation. It is necesary that the temperature and pressure ofdistillation be such that substantially no decomposition of the desiredresinous product takes place.

In a modification of the present invention in which a lighter resinousproduct is produced tfie acid-soluble oil fraction containing resinousmaterial is hydrogenated prior to distillation or, alternatively, theresinous product obtained from the distillation is hydrogenated. In thelatter case where the solid resinous product of the distillation step ishydrogenated, the solid products may be dissolved in a suitable solventto enable its flow through the hydrogenation step. Hydrogenation iseffected in the presence of a hydrogenation catalyst, such as molybdenumsulfide, nickel and the like, and in the presence of hydrogen. Aresidence time of from about 0.5 to about 5 hours is used, and atemperature between about 200 and about 750 F. and a pressure betweenabout 1,000 and 2,500 pounds per square inch gage are appropriate. Thedegree of hydrogenation should be sufficient to reduce color but notenough to alter subtantially the hardening properties of the resins. Thedecolorized product obtained by the hydrogenation of the acid-solubleoil fraction is distilled to remove volatile components and to leave asolid resinous material of a lighter color and of improved quality fromthat obtained with- When the solid resinous product obtained from thedistillation of the original acid-soluble oil fraction is hydrogenated,no distillation of the hydrogenated product is required unless'a solventhas been used.

The acid-soluble oil fraction which is distilled to produce a'solidresin product in the manner heretofore described has'an A.'P. I. gravitybetween about' 15 and about 30 degrees and an iodine number (ameasurement of unsaturation) between about 100 andV about 175.

"understood by referenceV to the accompanying lequipment may be providedby one skilled in the art without departing from the scope of thisinvention.

In this invention as applied to the alkylation of an alkylatablehydrocarbon, such as isobutane. with an olefin in the presence of afiuorine-containing catalyst, v such as hydrogen fluoride, a

'suitable and typical feed stockfor the hydroiluoric acid alkyiation inwhich the acid-soluble oils are a by-product appears in Table Il below:

Such a hydrocarbon feedenters reaction zone 9 as a liquid through lines4 and 6 and is intimate- A'ly contacted with liquid hydrofluoric acid,which yenters through line 8 and which vhas a titratable acidity ofabout 80 to about '95 per cent by Weight.

iThe'overall mol ratio of isoparafiin to olefin is usually from about14:1 to about 320:1 fin the combined feedand recycle (line 26) and muchhigher inthe reaction Zone. The time 'of residence lof the reactionmixture in the reaction Zone 9 is usually from about to about 15.minutes but it may be for shorter or longer periods as desired. Thevolume ratio of .acid to hydrocarbon is between approximately 0.5:1 andabout 2:1, generally about 1:1,.although other ratios may be maintained.The hydrocarbon feed stock enters the alkylation process at atemperature of about 8O tob about 100 and a pressure of about 90 to 100pounds persquare inch gage. Should it be desired however, both higherpressures and higher temperatures may be used. In general, onlysuflicient pressure to `assure liquid phase .operation is necessary.From reaction zone B a hydrocarbon conversion effluent is passed by lineI I to separation zone I2 in which the effluent separates into twoliquid phases, namely, a lighter 'hydrocarbon-rich phase and a heavierhydrogen :"iiuorideerich phase. The hydrogen fluoride-rich phaseiswithdrawn from the bottom ci' separation z'one |2.through line |3.tobe recycled as a catalyst for the alkylation reaction through lines I6and 5.8i Fresh .make-up: hydrofiuoricy acid may be ."added tothesystemthrough line 8, when desired. Since itzis desirable to removewater and acid- `soluble oils from the acid phase in order to assure theproper function of the catalyst as well as to recover acid-soluble oilsas a by-product`,"a portion or all of the hydrogenfiuoride phase ispassed to a purification unit 3|, the operation of which will bediscussed hereinafter. In purification unit 3|- Water and acid-solubleoils are removed through lines 33 and 34, respectively. A puriedanhydrousY acid phase is passed from purification unit 3| through lines32 and 8 to the reaction zone SQ L The liquid hydrocarbon-rich phasepasses from separation zone I 2Mthrough line I4 to azeotrope tower I8.Separation of a vaporous azeotropic lmixture of hydrocarbon and hydrogenfluoride -from the hydrocarbon phase' is effected in azeotrope tower 8.The azeotropic mixture passesv as a vapor from tower |8 through line I9shown). The organic fluorine compounds, which are formed asby-productsof the hydrocarbon lr `convers ion, -are removed by treatmentwith the j p The liq d hydrocarbon stream. 'substantially -freefrom'organic iiuorine compounds, passes through line 22 to fractionatingsystem 23, which may represent either a single deisobutanizer or aseries of fractionators for the separation and recovery of the variousproducts of the hydrocarbon conversion. The liquid hydrocarbon stream inline 22 has approximately the composition shown in Table III at thispoint in the process.

Table III .Hydrocarbon component: Mol per. cent Propane and lighterhydrocarbons 1 Isobutane y 1 -Q 57 Normal butane `1 20 Alkylate 22 Arelatively light hydrocarbon fraction is removed'from'fractionationsystem 23 through line 24. This light fraction removed through line '24comprises propane and lighter hydrocarbons and maybe vented or used asfuel. Another fraction containing primarily isobutane is removed from'fractionating system 23 through lineV 26 and is recycled to reactionzone` 9. A normal butane fraction is removed from fractionation system23 through line 21 and may be utilized as a fuel, etc., or passed to anisomerization system (not shown) for the isomerization of the normalbutane to isobutane for use in the alkylation reaction. The alkylationproduct of the process is withdrawn from fractionation system 23 throughline 28. This alkylation product comprises a relatively light alkylatefraction containing isooctanes, heptanes and hexenes, and a relativelyheavy alkylate by-product fraction. The heavy alkylate by-product may beseparated from the light alkylate product in another fractionation zone(not shown) Purification unit 3| may comprise any suitabl method andapparatus known to those skilled in the art for the removal andseparation of water and acid-soluble oilsfrom the acid phase. Unit whichthe acid-soluble oils are removed together --With water as a bottomproduct. "The properties of atypical acid-soluble oil fractionrecoveredfrom purification unit 3| through line 34 is shown in Table Ihereinbefore. The acid-soluble oil fraction constitutes about 8 to about9 weightl per cent of the total acid phase. y

v In accordance with this invention an acid-soluble oil fraction, suchas that recovered from puriilcation unit 3|, is passed through lines 36or 34, 38 and 4| to fractionation unit 42, in which fractionation unitlthe acid-soluble oil fraction is distilled to remove volatileconstituents through overhead line 43. The bottom product offractionator 42 which comprises the resinous product of this inventionis withdrawn therefrom through lines 44, 48 and 5|. Under the conditionsof subatmospheric pressure and elevated temperatures beingused infractionator 42 this bottom product is in the liquid phase but whencooled to atmospheric conditions it becomes a solid. Fractionator 42 isoperated at a pressure between about 5 and about 15 mm. 'of mercury andat a kettle .temperature between about 350 andabout 600 F.

According to the modification of this invention in which hydrogenationis employed, an acid-soluble oil phase from purification unit 3l ispassed through lines 34 and 36 to hydrogenation unit 39. Theacid-soluble oil fraction is hydrogenated in the presence of a catalyst.such as nickel, and in the presence of hydrogen. which enters throughline 31, at a temperature between about 200 and 750 F. and a pressurebetween 1,000 and 2,500 pounds per square inch gage. As previouslydiscussed, the residence time is between about 0.5 to about 5 hours.Hydrogenation products from unit 39 are passed through line 4I tofractionator 42 where the hydrogenation product is distilled to recovera resinous product. VVolatilecomponents are withdrawn from fractionator'42 through line 43 and the resinous product is drawn from the bottomthrough lines, 44, 48 and El. Y

In some instances it may be more desirable to rst distill and removevolatile components from the acid-soluble oil fraction from unit 3i andthen hydrogenate the resinous bottom fraction from the distillation. Insuch a case, acid-soluble oils from unit 3| are passed through lines 34and 4I, to fractionator 42, by-passing unit 39 via line 38. As before,volatile components of the acid-soluble oil fraction are withdrawn fromfractionator 42 through lines 43 and a resinous bottom product iswithdrawn from fractionator 42 through line 44. In many cases theresinous product Withdrawn from fractionator b42 through line 44 will bea solid or at least a very viscous material under the conditions ofhydrogenation. This bottom fraction may, therefore, be dissolved in asolvent which passes into line 44 through line 46. The resulting liquidmixture is then passed to hydrogenation unit 41 through line 44 where itis hydrogenated in the presence of a catalyst and in the presence ofhydrogen, which enters through line 49. The hydrogenated resinousproduct from hydrogenation unit 41 is withdrawn through line 5| and whennecessary excess solvent and volatile components are removed bydistillation (not shown). In this latter modification of the presentinvention it is frequently unnecessary to dilute the bottom resinousfraction from fractionator 42 with a solvent since this fraction isoften a liquid at the hydrogenation conditions of unit 41 anddistillation of the hydrogenated resinous product withdrawn through line5I is eliminated. The product obtained by the combination ofdistillation and hydrogenation is of a lighter color and improvedquality compared to the product obtained without hydrogenation but withdistillation alone.

The following examples are offered for a better understanding of thenature and applicationof invention and are not considered unnecessarilylimiting to the invention.

EXAMPLE I Isobutane was alkylated with butylene in the presence ofhydrofiuoric acid at about 90 F. and under a pressure of about 100poundsper square inch gage to produce an alkylate product boiling withinthe gasoline range. The overall mol ratio of isobutane to butylene wasabout 6:1 and the contact time about 10 minutes; the volume ratio ofhydrocarbon to acid was about 1:1 and the acidity of the acid phase wasabout 85 to 90 weight per cent. Acid-soluble `oils amounting to about 10per cent of the acid phase were recoveredand vacuum distilled with thefollowingresuits which are typical of the distillation properties ofsuch fractions.

[V acuuni distillation corrected to 760 mm. pressure.)

Vol. Overhead Per Cent Temp., Distilled F.

EXAMPLE II Composition of hydrocarbon feed, wt. per cent Propane 0.1Isobutane 42.6 Normal butane 1.1

Hexenes 8.5

Hexanes 21.3 Heptenes 2.9 Heptanes 5.5 Octenes 3.7 Octanes 9.7

Nonenes 0.6

Nonanes 2.3 Decenes and undecenes 0.1 Decanos and undecanes 0.8 Eea-vierhydrocarbons 0.8

Average mol. wt. of oleiins 95.4

Mol. ratio of isobutane to olefln 4.4 Temp., F 91 Pressure, p. s. i. gContact time, minutes 10.3

Vol. ratio of acid to hydrocarbon 1.15:1 Acidity of acid phase, wt. percent 81 Acid-soluble oil, wt.'per cent of acid phase- 10.4

The recovered acid-soluble oil was vacuum distilled with the followingresults:

[Vacuum distillation corrected to 760 mm. pressure.)

Overhead Vol.

Temp., Per Cent F. Distilled EXAMPLE III Four samples of acid-solubleoil fraction from an HF alkylationxprocess were distilled under Table,IV

Iodine N o.z Yield, Distilla- Softenf 'Sample Wt. Per tion ing A h o.Cent of Temp., Point, %hour 1 hour s 10 'Charge F. F.1 Absorp-Absorption, tion 38 392 .110 155 165 Trace 27 450 131 155 170 D0. 23 550l 138 160 170 D0. 11 570 --163 y 16o 17o Do. 1 5

1Ringandba11method-A-s.ritjes-2e.

2 Wijs method-grams of iodine per 100 ams of sample.

The material distilled overheadfrom the acidsoluble oil fraction wascolored at the beginning of the distillation and became brownish-greennear the end of vthe distillation... At the end of the distillation inwhich the oil was reduced to 23 and 17 weight per cent of the charge, a.very viscous pale green materialwas distilled over- 2 5 head. Thismaterial is not a solid resin at room temperature. The iodine numberofthe lowboiling oils inthe overheadisof theorder of 15o n.175... Y

A comparison of the iodine number of 167 for 30 the charge asexemplified in Table I with that of 155 to 160 of the resinous productshows a slight decrease in the iodine number of the resinous product asis determined by the pure oil modification of the Wijs method. Thismethod speciiies an absorption period of one-half hour. The iodinenumbers are also listed for one hour absorption, the time specified inA. S. T. M. D15443 for the determination of iodine number of oleoresinsby the Wijs method. The softening point is increased as the yield ofresins is decreased. It is estimated that a yield of 20 weight per centof the charge would produce a resin with a softening point of about 150F.

The resins are clear and brown in color, slightly darker than a dark tanof wood resin. An attempt to compare the resins with color standardsused in determining the color of oleoresins (A. S. T. M. D-154-43) showsthe resins darker than No. 5, even in a solution of approximately 25 50per cent resin in pentane. Sample l was a plastic, slightly tackymaterial. Samples 2, 3 and 4 were solid brittle material; however,resins 2 and 3 were slightly tacky. This would indicate that a resin of20 or less weight per cent yield would 55 have the properties ofbrittleness and non-tackiness. The ash of which there was less than 0.1per cent in the resin, had the appearance of iron oxide and gave aqualitative test for iron when dissolved in hydrochloric acid. Theacidity of the resin samples was negligible.

EXAMPLE IV EXAMPLE V A light-colored resin was produced by contacting anacid-soluble oil fraction from a hydrouoric acid alkylation process withhydrogen and a nickel-on-kieselguhr catalyst at about 390 F. 'I5

iora periodof about 3 hours. A light yellow oil wasobtainedfrom thecatalytic hydrogenation and rwas fractionaly distilled under reducedpressure to recover a,- light-colored resinous kettle 5 product(amounting to about 33 per centof'the original material). Thehydrogenated resin was lighter than No. 1 in a solution of about 25 percent resin in pentane according to the standard test method A. S. T. M.D-154-43.

The product obtained by distillingthe original acid-soluble oil fractionat reduced pressure was Very dark in color, being betweenNoi'j5 and No.6 in a solution of about 25 per cent resin in pentane according' tomethod A. S'.T', M`. D-154-'43. j Although"thi s' invention has beendescribed A With particular reference to the hydr'ocarbonconfyersioncarried out in the -particular manner, v,various modications andapplications will-"become apparent to those skilledin the art 'which maybe', practiced without departing from the scope of this invention.

Iclaim: Y l. A process for producing a solid hydrocarbon resin whichcomprises passing an acid-soluble oil fraction obtained from thecatalyst phase of a process forthe alkylation of an alkylatablehydrocarbon in the'presence of a catalyst comprising hydrofluoric acidto a hydrogenation zone', hydroge'nating the acid-soluble oil fractionin the presence of a hydrogenation catalyst-under hydrogenationconditions of temperature and pressure of about 200 to about 750 F. andabout 1,000 to about 2,500 pounds per square inch gage, distilling theeffluent of said hydrogenation under conditions of temperature andpressure such that at least 55 per cent of the eiiluent is distilledoverhead, and recovering a normally solid hydrocarbon resin as a bottomproduct of said distillation.

2. A process for producing a solid hydrocarbon resin which comprisespassing an acid-soluble oil fraction obtained from the catalyst phase ofa process for the alkylation of an alkylatable hydrocarbon in thepresence of a catalyst compris- -ing hydrofiuoric acid to ahydrogenation zone,

hydrogenating the acid-soluble oil fraction in the presence of ahydrogenation catalyst under hydrogenation conditions comprising atemperature within the range of 200,to 750 F. and a pressure within therange of 1000 to 2500 pounds per square inch gage, distilling theeiliuent of said hydrogenation under conditions of temperature andpressure, and recovering a normally solid hydrocarbon resin as a bottomproduct of said distillation.

3. The solid resinous product resulting from the process of claim 1.

4. The process for producing a solid hydrocarbon resin which comprisesdistilling an acidsoluble oil fraction, obtained `from the acid phase ofan alkylation process using a hydrouoric acid catalyst, under asubatmospheric pressure less than about mm. of mercury and at a kettletemperature between about 350 and about 600 F. to remove volatileconstituents, recovering a resinous bottom fraction from saiddistillation, hydrogenating said resinous bottom fraction in thepresence of a hydrogenation catalyst under hydrogenation conditions of atemperature between about 200 and about 750 F. and at a pressure betweenabout 1,000 and about 2,500 pounds per square inch gage, and recoveringa normally solid resinous product from said hydrogenation as a productof the process.

5. The process for producing a solid hydrocarbon resin which comprisesdistilling an acidsoluble oil fraction, obtained from the acid phaseartemisiav of an alkylation process using ahydrouoric acid catalyst,under a subatmospheric pressure to removeV volatile constituents,recovering a resinous bottom fraction from saidy distillation,hydrogenatingsaid resinous` bottom fraction in the presence of a`hydrogenation catalyst under hydrogenation conditions of. a temperaturebetween about 200 and about 750er F. and at a pressure between about1,000 and about 2,500 pounds per square inch gage, and recovering anormally solid resinous product from said hydrogenation as a product ofthe process.

6. The process for producing a solid hydrocarbon resin which comprisesdistlling an acidsoluble oil fraction, obtained from the acid phase ofan alkylation process using a hydrofluoric acid catalyst, under asubatmospherc pressure less than about 100 mm. of mercury and at akettle temperature between about 350 and about 600 F. to remove volatileconstituents,A recovering a resinous bottom fraction from saiddistillation, hydrogenating said resinous bottom fraction in thepresence of a hydrogenation catalyst under hydrogenation conditionscomprising a temperature within the range of 200 to 750 F. and apressure within the range of 1000 to 2500 pounds per square inch gage,and recovering a normally solid resinous product from said hydrogenationas a product of the process.

7.A The solid resin resulting from the process of claim 4.

8. A process for producing a solid hydrocarbon resin which compriseshydrogenating an acidsoluble oil fraction, obtained from the acid phaseof an alkylation process using a hydrofluoric acid catalyst, in thepresence of a hydrogenation catalyst under hydrogenation conditionscomprising a temperature within the range of 200 and 750 F. anda-,pressure within the range of 1000 and 2500 pounds per square inchgage.

LLOYD CLAYTON MORRIS.

REFERENCES CITED The following references are of record in the le ofthis patent:

UNITED STATES PATENTS Number Name Date 2,092,889 Mikeska Sept. 14, 19372,152,533 Carmody Mar. 28, 1939 2,180,367 Rostler Nov. 21, 19392,293,208 Lazar Aug. 18, 1942 2,301,335 Showalter et al. Nov. 10, 19422,392,962 Abrams Jan. 15, 1946 2,404,393 Mayland July 23, 1946 2,440,459Bloch Apr. 27, 1948 2,440,477 Johnstone Apr. 27, 1948

1. A PROCESS FOR PRODUCING A SOLID HYDROCARBON RESIN WHICH COMPRISESPASSING AN ACID-SOLUBLE OIL FRACTION OBTAINED FROM THE CATALYST PHASE OFA PROCESS FOR THE ALKYLATION OF AN ALKYLATABLE HYDROCARBON IN THEPRESENCE OF A CATALYST COMPRISING HYDROFLUORIC ACID TO A HYDROGENATIONZONE, HYDROGENATING THE ACID-SOLUBLE OIL FRACTION IN THE PRESENCE OF AHYDROGENATION CATALYST UNDER HYDROGENATION CONDITIONS OF TEMPERATURE ANDPRESSURE OF ABOUT 200 TO ABOUT 750* F. AND ABOUT 1,000 TO ABOUT 2,500POUNDS PER SQUARE INCH GAGE, DISTILLING THE EFFLUENT OF SAIDHYDROGENATION UNDER CONDITIONS OF TEMPERATURE AND PRESSURE SUCH THAT ATLEAST 55 PER CENT OF THE EFFLUENT IS DISTILLED OVERHEAD, AND RECOVERINGA NORMALLY SOLID HYDROCARBON RESIN AS A BOTTOM PRODUCT OF SAIDDISTILLATION.